Solid-state polymerization of long-chain vinyl compounds. II. Effect of molecular arrangement on polymerizability of octadecyl acrylate

To clarify the effect of a molecular arrangement of long-chain monomers on polymerizability, γ-ray-initiated postpolymerization of polymorphic crystals of octadecyl acrylate and the melt has been investigated. According to thermal, x-ray, and infrared (IR) analyses octadecyl acrylate exhibit three crystalline modifications similar to, but different in transition behavior from, those of octadecyl methacrylate. The α-form is stable in the range of 19–32°C (mp) and at lower temperatures the β-form is stable, whereas the sub-α-form appears transiently in α → β transition. The monomer molecules in triclinic packing (α-form) show little tendency to polymerize, whereas those in hexagonal packing (β-form) have high polymerizability that increases with temperature. The polymerizability in the molten state at fairly high temperatures is rather low, however. Thus the polymerization rate, saturated conversion, and polymer molecular weight exhibit maxima just above the melting point of α-form. It is concluded that the hexagonal packing of monomer molecules with particular orientation in the layered structure and rotational freedom around the molecular axis, together with some conformational freedom of functional group, is favorable to the polymerization reaction. In addition, the mechanism of polymerization in the layered structure is discussed, assuming a cone-type distribution for the polymerization probability.     

Solid-state polymerization of long-chain vinyl compounds. IV. Effects of chain length on the polymorphic behavior and postpolymerization of n-alkyl methacrylates

Polymorphic behavior and γ-ray-initiated postpolymerization of the even-numbered long-chain Methacrylates (C₁₈-C₁₂) have been investigated. Phase transition behaviors of octadecyl, hexadecyl, tetradecyl, and dodecyl methacrylates are respectively, which become simpler with shortening of the chain length. The methacrylate monomers with sufficiently long hydrocarbon chains, such as octadecyl and hexadecyl, can be polymerized rapidly in the α-form crystal (hexagonal packing) by a fully two-dimensional mechanism, whereas in the β-form crystal (triclinic packing), polymerization can hardly occur. In the case of dodecyl methacrylate, however, an accelerated polymerization in the β form occurs after an induction period of several hours and the resultant polymer is gel-like. This can be interpreted by the propagation reaction across the polymer chain already formed. It has been found that the solid-state post-polymerization of n-alkyl methacrylates is affected by the chain length through the packing mode of the monomer molecules and also by the aggregation state of side chains in the resultant comblike polymer.     

Solid-state polymerization of long-chain vinyl compounds. III. Mechanism of γ-ray-initiated postpolymerization in layered structures of octadecyl methacrylate and acrylate

The mechanism and kinetics of the γ-ray-initiated postpolymerization of octadecyl methacrylate and acrylate in lamellar crystals were investigated by a simple model. This model assumes that the initiation points are distributed as in a checkerboard and that polymerization probability of the monomer molecules decreases conically around each initiation point. The two-dimensional polymerization can be characterized in this cone model by two parameters, a and r; a represents the polymerizability of the monomer for a given condition, and r depends on the number of initiation points per unit area. G values for the initiation reaction of octadecyl methacrylate and acrylate were estimated as 0.8 and 1.6, respectively. The two-dimensional postpolymerization of long-chain compounds proceeds in two stages. The rate of polymerization is very high and zero order with respect to monomer concentration in the first stage. It is lower and obeys first-order kinetics in the second stage. The rate constants of the zero-and first-order polymerizations were k_p0 = 1.73 molecule sec^-1 and k_p1 = 0.93 sec^?1, respectively, for octadecyl acrylate at 20°C.     

Polyreactions in ordered systems: Polymerization of octadecyl methacrylate in monolayers at the gas–water interface

The ultraviolet-initiated polymerization of octadecyl methacrylate (ODMA, octadecyl 2-methyl-2-propenoate) as a monomolecular layer at the gas-water interface was studied. The polymerization was carried out at 27°C at the nitrogen-water interface; air inhibits the polymerization. At 27°C the ODMA monolayer exhibits three different states which were characterized by surface pressure-area diagrams and by surface potential measurements. The ODMA monolayer was polymerized under constant surface pressure in the range between 0 and 10 dyne/cm. The polymerization was followed by recording the contraction of the film. The conversion was determined by comparison of the area per monomer unit during polymerization with the area of mixed monolayers formed from ODMA and poly-ODMA as well as by infrared spectroscopy. The polymerization in the condensed state of the monolayer (at high surface pressure) is considerably faster than in the expanded state (at low surface pressure). As the polymer has a condensing effect on the monomer in the mixed monolayer, autocatalysis is suggested at low surface pressures. The resulting polymer was studied by x-ray diffraction. The structure of the freshly collapsed film is determined by the conformation of the polymer at the interface; the data after crystallizing the same sample from the melt point to higher tacticity of the poly-ODMA prepared in monolayers than that of poly-ODMA prepared by normal radical polymerization in solution.     

Radiation-Induced Solid-state Polymerization in Some Methacrylates

This paper presents a comparison of some of our results on the polymerization of methacrylic acid, octadecyl methacrylate, zinc methacrylate, and barium methacrylate monohydrate in the solid state. Polymerization was initiated by cobalt-60 γ rays, both in-source and post-irradiation polymerization techniques being used. Electron spin resonance studies showed that the polymerization proceeded by a free radical mechanism in all cases. The initial radicals formed by irradiation at low temperatures added a first monomer unit about 100° below the temperature of long-chain polymerization. Some radical decay occurred in the early stages of polymerization. The rate of polymerization increased rapidly, approaching the melting point or other phase change in the monomer.     

Effects of chlorophosphines on the radical polymerization of methyl methacrylate

The effect of chlorophosphines (phosphorus trichloride, dichlorophenylphosphine, chlorodiphenylphosphine) on the radical polymerization of methyl methacrylate was investigated in benzene solution. The polymerization was carried out at 50°C by the standard solution method, α,α′-azobisisobutyronitrile being used as an initiator. These chlorophosphines accelerated the polymerization of methyl methacrylate but did not affect the rate of decomposition of α,α′-azobisisobutyronitrile. Ultraviolet and infrared spectral data suggested that the acceleration effect was due to the complex formation of methyl methacrylate with each chlorophosphine. From the result of a copolymerization with styrene, it was found that the reactivity of methyl methacrylate monomer increased in the presence of dichlorophenylphosphine.     

γ-Ray-induced polymerization of α-haloacrylic acids

The γ-ray induced polymerizations of α-chloroacrylic acid, mp 66°C, and α-bromo-acrylic acid, mp 72°C, were investigated in the temperature range from 35°C to 85°C. An analysis of polymerization kinetics was made, and results were similar to those reported in the literature for other vinyl monomers. On heating of the polymer obtained, elimination of hydrogen halide takes place, and intramolecular lactone formation is observed. The rate of lactone formation of poly(α-chloroacrylic acid) obtained in the solid-state polymerization was found to be higher than that in the liquid state, because a highly isotactic configuration of polymers, tends to be formed in the solid-state polymerization, and elimination of hydrogen chloride is facilitated with an isotactic 5₂ helix structure.     

Viscosity effects in cobaloxime‐mediated catalytic chain‐transfer polymerization of methacrylates

The effect of bulk viscosity on the cobaloxime‐mediated catalytic chain‐transfer polymerization of methacrylates at 60 °C was investigated by both the addition of high molecular weight poly(methyl methacrylate) to methyl methacrylate polymerization and the dilution of benzyl methacrylate polymerization by toluene. The results indicate that the bulk viscosity is not directly linked to the chain‐transfer activity. The previously measured relationship between chain‐transfer‐rate coefficient and monomer viscosity therefore probably reflects changes at the molecular level. However, the results in this article do not necessarily disprove a diffusion‐controlled reaction rate because cobaloxime diffusion is expected to scale with the monomer friction coefficient rather than bulk viscosity. Considering the published data, to date we are not able to distinguish between a diffusion‐controlled reaction rate or a mechanism directly affected by the methacrylate substituent. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 782–792, 2002; DOI 10.1002/pola.10152     

Solvent-free polycondensation of 1,3-bis(hydroxyphenylmethyl)benzene. II. The dramatic difference in the polymerization behavior between meso and racemic isomers

The meso and racemic forms of 1,3-bis(hydroxyphenylmethyl)benzene underwent solvent-free polycondensation with the aid of an acid catalyst giving polyether. Very interestingly, the diastereoisomerism caused a considerable difference in the polymerization behavior. The meso isomer (mp = 96–98 °C) was polymerized even at 65 °C, whereas the racemic one (mp = 158–160 °C) required heating at 100 °C to undergo polymerization. However, the latter produced a much higher molecular weight than the former (30,000 vs 4000). The contamination of the meso isomer with the racemic one very sensitively reduced the polymerization temperature: the 98.5% meso monomer underwent polymerization at 50 °C. In contrast to solvent-free polymerization, two diastereomeric monomers showed almost identical behavior in solution polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3564–3571, 2003     

Sulfur-Containing Vinyl Monomers. XV. Kinetic Study of Radical Polymerization of Vinyl Mercaptobenzothiazole and Its Copolymerization

A kinetic study of radical polymerization of vinyl mercaptobenzothiazole (VMBT) with α,α′-azobisisobutyonitrile (AIBN) at 60°C was carried out. The rate of polymerization (R_p) was found to be expressed by the rate equation: R_p = k[AIBN]^0.5 [VMBT]^1.0, indicating that the polymerization of this monomer proceeds via an ordinary radical mechanism. The apparent activation energy for overall polymerization was calculated to be 20.9 kcal/mole. Moreover, this monomer was copolymerized with methyl methacrylate, acrylonitrile, vinyl acetate, phenyl vinyl sulfide, maleic anhydride, and fumaronitrile at 60°C. From the results obtained, the copolymerization parameters were determined and discussed.     

Solid-state polymerization of long-chain vinyl compounds. VI. In-source polymerization of octadecyl acrylate by γ-ray irradiation

The in-source polymerization of octadecyl acrylate in the lamellar crystal (hexagonal packing) by γ-ray irradiation has been investigated, as compared with the two-step and one-step postpolymerizations. The viscosity-average molecular weight is very high even in the initial stage and is practically saturated after 3–5 hr, although the conversion increases successively with time. The molecular weight distribution of poly(octadecyl acrylate) obtained by in-source polymerization is very wide (M _w/M _n = 13.1, at 20°C). The results of in-source polymerization of the long-chain vinyl compounds can be interpreted using the cone model for polymerization probability, similar to those of one-step and two-step postpolymerizations.     

甲基丙烯酸丁酯在Nd-Al-α,α'-联吡啶催化剂体系中的聚合反应

 研究了Nd（naph）3－Al（i－Bu）3－α,α’－联吡啶（naph＝环烷酸）催化体系中甲基丙烯酸丁酯的聚合反应．用核磁共振和红外光谱表征了聚合物的结构．用凝胶色谱测定了聚合物的分子量和分子量的分布．结果表明,聚合物的结构以全同和无规为主,反应机理为配位聚合,聚合反应对单体浓度呈一级关系,表观活化能为30．2kJ／mol．     

Ultrasonic Modification of Polymers. II. Degradation of Polystyrene,Substituted Polystyrene,and Poly(n-vinyl Carbazole) in the Presence of Flexible Chain Polymers

Abstract

Ultrasonic (20 kHz, 70 W) solution degradations of polystyrene, substituted polystyrenes, and poly(n-vinyl carbazole) have been carried in toluene and tetrahydrofuran at 27 and -20°C in the presence of flexible chain polymers. Polystyrene formed block copolymers at 27°C with stiff-chain polymer PVCz; however, in the presence of flexible chain polymers, e.g., poly(vinyl methyl ketone) or poly(vinyl methyl ether), there were no block copolymers formed. Poly(n-vinyl carbazole) does not seem to form any block copolymers at 27°C with flexible chain polymers, e.g., poly(octadecyl methacrylate) and poly(ethyl methacrylate). Poly(p-chlorostyrene) and poly(p-methoxystyrene) also do not form block copolymers at 27°C with poly(octadecyl methacrylate) but do so with poly(hexadecyl methacrylate). It is quite possible that these may only be blends of two homopolymers. Poly(octa-decyl methacrylate) does yield a block copolymer when sonicated at -15°C with poly(p-isopropyl α-methylstyrene).     

Poly(β-amino acid)s. IV. Synthesis and conformational properties of poly(α-isobutyl-L-aspartate)

Poly(α-isobutyl-L -aspartate) was prepared by the polycondensation reaction of p-nitrophenyl ester of α-isobutyl-L -aspartate and the conformation of the poly(β-amino acid) was investigated by X-ray diffraction, polarized infrared, circular dichroism (CD), optical rotatory dispersion (ORD), and NMR spectroscopy. α-Isobutyl β-p-nitrophenyl-L -aspartate hydrochloride and hydrobromide were used as monomers and dimethylformamide, chloroform, and chlorobenzene, as solvents. A high-molecular-weight polymer with [η] 1.0 dl/g (dichloroacetic acid, 25°C) was formed in the polymerization of the hydrochloride in chloroform at 25°C. The X-ray diagram and polarized infrared spectrum of the stretched polymer film obtained from a chloroform solution suggested a cross-β-form as the most probable structure in the solid state. The CD spectra of the polymer in a 2,2,2-trifluoroethanol (TFE) solution and its film cast from the solution showed a peak at 205 nm and a trough at 190 nm which were assigned to a β-structure. The polymer was associated in chloroform. The NMR and ORD spectra in chloroform were similar to those in TFE, which suggests that the polymer also exists in the β-structure in chloroform. The addition of small amounts of dichloroacetic acid and sulfuric acid to chloroform and TFE solutions, respectively, destroyed the β-structure. A random copolymer of α-isobutyl-L -aspartate with β-alanine was also prepared by polycondensation reaction. The copolymer apparently did not form an ordered structure in the solid state or in solution.     

Beziehungen zwischen Lumineszenzspektrum und Struktur von Seltenerdkomplexen. III. Zur Existenz unterschiedlicher Polyedertypen bei Alkalitetrakis(dibenzoylmethanato)europat(III)-Komplexen

The luminescence spectra of alkali tetrakis(dibenzoylmethido)europate(III) complexes in the crystalline state at 77°K have been measured in the spectral region 510–640 nm. The spectra show the existence of different modifications of these compounds. The spectra of the β-forms are consistent with a site symmetry D₂ at the Eu(III) ion, the spectra of the corresponding α-forms with a site symmetry D₄. A conversion from the β-form into the α-form on heating is observed in some cases. The conversion involves a change from dodecahedral into antiprismatic coordination around the Eu(III) ion.     

成核剂含量对β晶相聚丙烯结晶与熔融行为的影响

用DSC研究了β成核剂含量对β聚丙烯在等温与非等温结晶条件下的结晶与熔融行为的影响,发现当成核剂含量为0.005％时,结晶焓△H_c、β晶的熔融焓△H_(mβ)及熔点T_(mβ)均为最大,而α晶的相对含量最小.广角X-衍射数据表明,成核剂含量高的试样的(301)衍射峰的相对强度下降,反映分子链排列的纵向有序性降低.根据聚丙烯分子在β成核剂上附生结晶的成核机理解释了上述结果.     

Equilibrium anionic polymerization of n-valeraldehyde

This paper describes an anionic polymerization of n-valeraldehyde (VA) in tetrahydrofuran (THF) initiated by benzophenone-monolithium complex in a high vacuum system. In spite of the deposition of the resulting polymer an equilibrium state between the monomer and the polymer was observed at a temperature range of ?90 to ?68°C. From the linear relationship between the equilibrium monomer concentration and the polymerization temperature, values of ?5.3 ± 0.3 kcal/mole and ?25.7 ± 1.4 cal/mole-deg, respectively, were evaluated for the enthalpy change and the entropy change in the present system. The effect of polar substituents on the polymerizability of aldehydes is discussed from the comparison of these values with those in the case of β-methoxypropionaldehyde.     

Ion‐exchanger synthesis using reversible addition‐fragmentation chain transfer polymerization

An ion‐exchanger with polyanionic molecular brushes was synthesized by a “grafting from” route based on “surface‐controlled reversible addition‐fragmentation chain transfer polymerization” (RAFT). The RAFT agent, PhC(S)SMgBr was covalently attached to monodisperse‐porous poly(dihydroxypropyl methacrylate‐co‐ethylene dimethacrylate), poly(DHPM‐co‐EDM) particles 5.8 μm in size. The monomer, 3‐sulfopropyl methacrylate (SPM), was grafted from the surface of poly(DHPM‐co‐EDM) particles with an immobilized chain transfer agent by the proposed RAFT protocol. The degree of polymerization of SPM (i. e. the molecular length of the polyanionic ligand) on the particles was controlled by varying the molar ratio of monomer/RAFT agent. The particles carrying polyanionic molecular brushes with different lengths were tested as packing material in the separation of proteins by ion exchange chromatography. The columns packed with the particles carrying relatively longer polyanionic ligands exhibited higher separation efficiency in the separation of four proteins. Plate heights between 130–200 μm were obtained. The ion‐exchanger having poly‐(SPM) ligand with lower degree of polymerization provided better peak‐resolutions on applying a salt gradient with higher slope. The molecular length and the ion‐exchanger group content of polyionic ligand were adjusted by controlling the degree of polymerization and the grafting density, respectively. This property allowed control of the separation performance of the ion‐exchanger packing.     

Reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in suspension

The reversible addition–fragmentation chain transfer polymerization of methyl methacrylate mediated by 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB) in bulk (60 and 70 °C) and suspension (70 °C) was studied, and in both polymerization systems, a good control of the molecular weight and polydispersity was observed. Stable suspension polymerizations were carried out over a range of CPDB concentrations, and with increasing CPDB concentration, the particle size and polydispersity index of the produced polymer decreased. The former was ascribed to the lower viscosities of the monomer and polymer droplets at low conversions, which caused easier breakup with the applied shear stresses. Lower polydispersity indices at higher CPDB concentrations were probably caused by a diminished gel effect, which was observed at lower CPDB concentrations at high conversions, causing a broadening of the molecular weight distribution. The livingness of the polymers formed in suspension was proven by successful chain extensions with methyl methacrylate, styrene, and 2‐hydroxyethyl methacrylate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2001–2012, 2005     

Polymerization of aromatic aldehydes. II. Cationic cyclopolymerization of phthalaldehyde

Phthalaldehyde was found to undergo cyclopolymerization with ease by several cationic catalysts and by γ-ray irradiation. The polymer was composed entirely of the dioxyphthalan unit, as confirmed by infrared spectroscopy and ready decomposition to monomer. The enhanced polymerizability of phthalaldehyde as compared with other aromatic aldehydes was explained in terms of the intermediate-type or, preferably, concerted propagation scheme. The conversion reached a saturation value of 87% in about 1 hr in methylene chloride at ?78°C, indicating an equilibrium polymerization. The ceiling temperature of the polymerization was ?43°C, as estimated from the relation between the saturation yield and polymerization temperature. The enthalpy and entropy of propagation were ?5.3 kcal/mole and ?23.0 eu, respectively. Since the molecular weight of the polymer was proportional to conversion, the propagating chain end was considered to be “living” in this system. The rate constant for propagation was calculated to be 0.18 1/mole-sec in methylene chloride at ?78°C with BF₃OEt₂ catalyst.